Treatment of oxidized hydrocarbon mixtures and products thereof



Patented Jan. 8, 1952 UNITED STATES PATENT OFFICE ration of Delaware NoDrawing. Application September 13, 1949; l Serial N0. 115,558

Claims.

dro'carbon mixtures may be obtained that have relatively lowsaponification values, e. g'., less than about 400 ings of KOH per gramand, hence, contain a substantial amount of monofunctional substances,e. g. monobasic acids, with a negligib'le amount, if any, of crystallinedifunctional substances. On the" other hand, and as is described morefully hereinafter, by varying the conditions under which the oxidationis eefi'cted, oxidized hydrocarbon mixtures may be obtained that haverelatively high saponification values, e. g., at least about 400 mgs. ofKOH per gram and substantially higher, e. g., on the order of 500 to 625or more. s uchoxidized hydrocarbon mixtures contain, in addition tomonofunctional substances, a substantial amount of crystallinedifunctional substances, e. g., dlbasic acids, and substancesconvertible thereto, the attainment of uch relatively highsaponifioation' values bein effective to convert a substantial amount ofthe hydrocarbons to polyfunctional in preference to monofunctionalsubstances. Generally speaking, such oxidized hydrocarbon mixtures,prepared by liquid phase oxidation of hydrocarbons by reaction thereofwith oxygen of a free-oxygen containing gas, and particularly when theoxidation is continued to relatively high saponification values, arecharacterized by having an acid value substantially lower than the saponification value and, in many instances, the difference between theacid andsaponification values often represents about 40% of thesaponification value.

In a n ing application Serial No. 625,961 (new U. S. Patent No.2,486,454), filed October 31, 1945, of which one of us is the inventor,a

method, and products resulting therefrom, has been described fortreatment of hydrocarbons in liquid phase under controlled conditions byreaction of the hydrocarbons with oxygen of a free oxygen-containinggas. An important aspect of the invention disclosed therein is that, byuse of the conditions disclosed, suppression of resinifition of crudeoxidation mixtures with minimized 7 formation of resinous materials atvarious stages of the oxidation but, of considerable importance, enablescontinuance of the oxidation to relatively high saponification values,e. g., over 400, whereby oxidized hydrocarbcn mixtures may be preparedthat contain a substantial amount of dibasic acids and polyfunctionalsubstances convertible thereto. In one illustration, the process of theaforesaid copending application comprises contacting hydrocarbons inliquid phase with a gas containing free oxygen at an oxidizingtemperature while controlling the rate of feed of the gas to thehydrocarbons and the gas distribution therein to maintain dispersed inthe hydrocarbons an amount of gas sufficient to cause combination ofoxygen at an average rate related to the oxidizing temperature asfollowsz' substantially above 1.5 liters of oxygen per hour per kilogramof hydrocarbons at an oxidizing temperature of (1, substantially above23 liters of oxygen per hour per kilogram of hydrocarbons at anoxidizing temperature of C., and substantially above 135 liters ofoxygen per hour per kilogram of hydrocarbons at an oxidizing temperatureof C.

Oxidized hydrocarbon mixtures, prepared in the manner disclosed in theaforesaid copending application, are characterized by having asubstantial difference between the acid and the saponification value,the components accounting for the difierential being largely composed ofpartially oxidized hydrocarbons of complex chemical structure. Due tothe presence of the stated partially oxidized substances largelyaccounting for the difference between the "acid and saponificationvalues of oxidized hydrocarbon mixtures prepared in accordance with themeth- 0d of the aforesaid application, such crude oxidized hydrocarbonmixtures present certain problems, as for example, with respect torecovery of desirable constituents thereof. In illustration, referenceis made to copending applications Serial No. 668,3'17 (now U. S. PatentNo. 2,43 ,455 filed May a, 1946-, and Serial No. 769,761 (now s. PatentNo. 2,486,456), filed August 2() 1947, of which one of us is theinventor, disclosing thermal and catalytic treatments for such crudeoxidized hydrocarbons to effect improved recovery of crystalline dibasicacids by suppressing the effect of the intermediately oxidized.hydrocarbons to inhibit recovery of crystalline polyfunctionalcomponents from the crude oxidized mixture.

Investigations directed to the use of oxidized hydrocarbon mixtures ofthe type disclosed in and prepare by the method set forth in copendingapplication Serial No; 625,961 (now U. S.

Patent No; 2,486,454), for recovery of certain desirable constituentsthereof has: revealed that oxidized hydrocarbon mixtures perform in anunexpected manner. Since such oxidized hydrocarbon mixtures contain asubstantial concentration of saponifiable constituents, consisting ofboth the compounds that account for the acid value as well as compoundsthat account for the difference between the acid and saponiflcationvalue, it is highly desirable to treat such oxidized hydrocarbons torecover saponifiable equivalents therefrom in highly useful form and ina simple and economic manner. Resort has type disclosed in and preparedby the method set mixtures.

In our copending application, Serial No. 107,138, filed July 2-7, 1949,a method has been disclosed for treatment of oxidized hydrocarbontherefore been made to use of conventional dismixtures, of the typedisclosed and prepared in tillation in an attempt to recover thesaponifiable the manner set forth in copending application value of suchoxidized hydrocarbon mixtures in Serial No. 625,961 (now U. S. PatentNo. distillate form but such attempts have revealed 2,486,454), toimprove the susceptibility of such that the amount of saponifiableconstituents in oxidized hydrocarbon .mixtures to distillation therecoverable distillate'or distillates totals sub- 5 ith improved reovery in desired distillate stantially less than the saponifiable valueof the form, of saponifiableequivalents present in t crude oxidizedmixture subjected to the distillaoxidized mixture. Briefly, the processdisclosed tion. In specific illus t on hereof, an O d therein comprisesreacting such crude oxidized hydrocarbon mixture, prepared by oxidizinga hydrocarbon mixtures with an organic compound scale :wax (105 to 108F. melting point) in the containing a hydroxyl group possessingalcoholic manner disclosed in copending application Serialcharacteristics to effect combination of sa- No. 625,961 (now U. S.Patent No. a ponifiable groups in the oxidized hydrocarbon having anacid value of 408.8 and a sapo fi mixture with an amount of thehydroxyl-bearing tion value of 632.8, was subjected to distillationcompound equivalent to at least a portion, based and the resultsobtained are set forth in Table I. on the acid value, of the oxidizedhydrocarbon In that table, the figur Of 9 S w as t mixture. As in theinvention described in coweight yield (based on the weight of theoxidized pending application Serial No. 107,138, the preshydrocarboncharge) and the 68.5% shown as ent invention embodies, for use asstarting mate- 'the weight of saponifiable equivalents recovered rials,oxidized hydrocarbon mixtures of the type in the distillate includes3.1% (by weight of disclosed in and prepared by the method set forthcharge) of an aqueous acidic solution recovered in copending applicationSerial No. 625,961 (now as distillate in a Dry Ice trap employed incarry- U. S; Patent No. 2,486,454). Furthermore, and ing out thedistillation, said acidic solution consimilar to the invention disclosedin Serial No. taining 3% of saponifiable equivalents based on 107,138,the present invention relates to treatthe saponifiable equivalents inthe charge. ment of such crude oxidized hydrocarbon mix- Table IDistillate yields Total yield Fraction up to 100 C. at Fraction froml00l75 C. Fraction from l75l97C.

0.2 mm. pressure at 1.0 mm. pressureat l to 3.2 mm. pres- Acid Value=333.7; Acid Va1ue=632.8; sureAcid Value= Sap. Value=6l0.4 Sap.Value=739.2 459.2; Sap. Value=652.4

g1? g ig Per Cent of Per Cent of Per Cent of 035 53 oi halg l Per Centby g p p fip fi- Weight of able Equivable Equivable Equiv- Charge ReiPer Cent alents Per Cent alents Per Cent alents covered as es by Weight(based on by Weight (based on by Weight (based on Distillates of ChargeSapomiiof Charge Saponifiof Charge Saponifl. and Botfi able EquivableEquivable Equivtoms g g-3 alents ill alents in alents in Charge Charge)g Charge) A 94.9 68.5 14.6 10.5 23.6 27.6 an 27.4 26.9% (hard, brittlemass I at 280 C. and 3.2 mm.

' pressure).

The data in the foregoing table shows a b 55 tures to improve thesusceptibility thereof to dissubjecting the crude oxidized hydrocarbonmixture; to distillation, 94.9% of the charge (by weight) was recovered,the 94.9% recovery being the sum of the distillates obtained plus thebottoms product (26.8%) which was a hard, brittle mass. Such asubstantial amount of bottoms product was formed even though thedistillation, carried .out to a bottoms temperature of 280 C. at 3.2 mm.pressure, was not sufficient to effect decomposition as, during thedistillation, no evidence of substantial, if any, evolution of carbondioxide was observed. However, and although the total products recoveredamounted to 94.9% .of the charge, the saponifiable equivalents of thecharge were recovered in desired distillate form in an amount of only68.5% based on the saponifiable equivalents content of the oxidizedhydro- .carbon; charge subjected to the distillation. It

is clear, therefore, as evidenced by the foregoing data, that oxidizedhydrocarbon mixtures of the tillation with improved recovery, indesirable distillate form, of saponifiable equivalents presentin theoxidized hydrocarbon mixture. Moreover, and as in the method set forthin Serial No. 107,138, the present invention is directed to treatment ofthe oxidized hydrocarbon mixture byreaction thereof with a suitablehydroxyl-bearing compound but differs therefrom in that, in acadvantageswhich Will be apparent from the more detailed description of theinvention set forth hereinafterp r a Broadly speaking, the presentinvention comprises an improved method for reacting a crude oxidizedhydrocarbon mixture, as aforedescribed,

with asuitable organic compound (containing a hydroxyl group possessingalcoholic characteristics) n the presence of asuitablecatalyst topromote combination between said oxidized hydrocarbon mixture and saidhydroxyl-bearing compound, and products of such a method. Although theinvention broadly contemplates use of hydroxyl-containing compounds asaforesaid, particularly suitable compounds are monohydroxyl-containingcompounds, illustrations of which include alcohols, and, moreparticularly,

aliphatic alcohols such as ethanol, methanol,

6. improvement in recovery of saponifiable equivalents from the oxidizedhydrocarbon mixture, thereby representing a marked improvement in theutilization of such oxidized hydrocarbon mixtures for recovery,particularly in highly desired distillate form, of the saponifiableequivalents thereof. As an important aspect of this invention, the useof a catalyst enables the obtainment of decided advantages in promotingor enhancbutanol, Z-ethylhexanol, octanol, and the like. ing continuedreaction of the oxidized. hydro- Hence, in the more detailed discussionof the carbons with the hydroxyl-bearing compounds invention set forthhereinafter, such alcohols in amount inexcess of the theoreticalequivalent have b p y d for illustrative, but not based upon the acidvalue of the oxidized hydrolimitative, purposes. In illustration, themethod carbons. That use of the catalyst provides such of this inventioncomprises reacting the crude 1;; results is clearly unexpected and isparticularly oxidized hydrocarbon with a suitable hydroxylso when it isconsidered, as is discussed more containing compound as aforesaid in thepresfully hereinafter, that such results are not as ence of a suitablecatalyst, the hydroxyl-bearing readily obtained in absence of thecatalyst. compound being employed in an amount in ex- In order tofurther describe the invention, sevcess of the theoretical equivalentbased on the go eral examples are set forth hereinafter presentacidvalue of the oxidized hydrocarbon mixture. ing data which, when comparedwith the results In preferred form, the invention embodies use in setforth for run No. 1 (Table I) clearly evidence the reaction of an amountof the hydroxylthe markedly improved results obtained by pracbearingcompound substantially in excess of the tice of this invention. As inrun No. 1, no evitheoretical equivalent based on the extent to 35 denceof substantial, if any, carbon dioxide for- Which it is desired toeffect combination with mation was observed in any of the examples setSeponifieble groups of the O idiz d hydrocarbon forth hereinafter duringdistillation of the prodmixture, and in more preferred form, the amountucts formed by reaction between the oxidized of the hydroxyl-bearingcompound employed is hydrocarbon mixtures and the hydroxyl-bearing atleast equal to, or in excess of, the theoretical compound, tillustrating t t t highly equivalent based on the saponifiable value ofthe proved results obtained by practicing this in Oxidized hydreeel'benm u e reac n betion were not obtained at the expense of effecttween theoxidized hydrocarbon mixture and the ing decomposition as would beindicated by carhydroxyl-bearing compound to obtain the results bondioxide formation. In the data set forth m di herein y suitably be f d vr a in Tables II to VII, the total yield by weight of rather widetemperature range as, for example, :large recovered as distillate andbottoms is from about C. to about 250 C. or even higher, based on thecharge to distillation of the alsuch as on the order of 275 C. or othertemperacoho] reacted oxidized hydrocarbon and the total ures as lo as,fo t particular oxidized hyyield of saponifiable equivalents in thedistillates droeerbon p y the reaction p atur 40 and bottoms is based onthe saponifiable. equivdoes not exceed that at which incipient orsubalents of the oxidized hydrocarbon mixture substantial decompositionof the oxidized hydrocarje ted to the alcohol treatment. be O C Altheughh higher temperatures An oxidized hydrocarbon mixture, identical to y,in some instances. b desirably empleyed, that used in Table I, was mixedwith an amount usa t r of s n t generally d d essential as is of butanoldouble the theoretical equivalent based hi hly ui bl resuIts may be ob nd by use on the saponification value of the oxidized hydroof lowertemperatures, as for example, about car-ban mixture and 10% (based onthe weight of C. to about 220 C. and the temperatures set forth saidoxidized hydrocarbon mixture) f concem the examplfas Set fort}?herelmPfter shqwme trated sulfuric acid. The resulting mixture wassuitable embodiments of this invention. As 1s set so heated for 10 hoursat to C and then at more l haematite". has been fmmd 124 to 133 c. for 32 hours with continuous withthat by sub ectmg such oxidized hydrocarbonmixtures to treatment with a hydroxyl-bearing f g firmed the reactwncompound (as aforedefined) in the presence of a fi ysls o e reac lonproduc 2) suitable catalyst, combination of the hydroxylamed therefmnshowed a the 9x10112601 hydro bearing compound may be effected to anextent carbon mlxture had combined with an amount in excess of thetheoretical equivalent based on of the alcohol equwalent to 139% basedon the the acid value to produce.products characterized acid Value Ofthe Oxidized hydrocarbon Inf fixturesby having an improvedsusceptibility t t t- Upon subjecting the reaction product todistillament by distillation, as compared to the oxidized it) tien, thefollowing e u ts Were obtained (Table hydrocarbon mixture per se, and toeffect an II):

Table II Distillate yields Total yield Fraction up to C. at Fractionfrom 170 to 2329 0.1 to 0.5 mm. pressure- 0. at 1.2 to5.0 mm. pres- AcidValue=9.5; Sap. sureAcid Value -15.1; Run N0 Value=392.0 Sap. VaIue=39L0v Bottoms %(l?131ra'1vigght based on by tidied stars gig i z g Per Centby Equivalents Per Qent by Equivalents covered as (based on Weight of(based on Weight of (based on Distillate Saponifiable Charge Ohfige andBotmms g l g f g l Charge) in Charge) 2 88.0 83. 5 66.8 67.2 14.. 9 16.36.4 (ahard brittle mass at 350? O. and

6.0 mm. pressure).

An oxidized hydrocarbon mixture, identical to that used in Table I, wasmixed with an amount of butanol double the theoretical equivalent basedon the saponification value of the oxidized hydrocarbon mixture. Themixture was heated for 6 hours at 86 to 93 C. during which gaseous HClwas bubbled through the reacting mixture with continuous withdrawal ofWater formed during the reaction. Analysis of the reaction productshowed that the oxidized hydrocarbon mixture had combined with an amountof alcohol equal to 118% based on the equivalent of the acid value ofthe oxidized hydrocarbon mixture. Distilla- Table IV Distillate yieldsTotal yields Fraction up 150 0. Fraction from 150-170" Fraction froml70-225 at 0.1 mm. pressure 0. at 0.1-2.0 mm. pres- C-. at 0.2-5.0 mm.pres- Acid Value=lfi.2; Sap. sure-Acid Value=4.5; sureAr-id Value=3.9;Value=421 Sap. Value=4l9 Sap. Value=386 Run Bottoms (Per Cent by Q C0 tbV ifiablc Per Cent Per Cent Per Cent Weght based on Charge) fiEqug'aleilits of of gagfnof Ifiaglon- P in isti- .iae lae iae P lates(based Percent by Equivalents Gem by Equivalents Per Cent b3 Equivalentscovered as on Sam} Weight of (based on V1 eight of (based on Weight of(based on gg ifiable Charge aponillable Chmge Saponifiable chargeSaponifiable ms Equivalents Equivalents Equivalents Equivalents o inoxidized in Charge) in Charge) in Charge) hydrocarbon Charge) 89. 2 83.7 36. 7 41. 0 12. 4 l3. 7 28. 5 29. 0 11.6 (hard brittle mass).

tion of the reaction product (run No. 3) gave the results set forth inTable III. A portion of the same reaction product was further heated at132 to 152 C. for 9 hours (run No. 4) with continuous withdrawal ofwater formed and analysis of the resulting product showed that theoxidized hydrocarbon had combined with an amount of butanol equal to129% of the theoretical amount based on the equivalent of the acid valueof the oxidized hydrocarbon mixture. Distillation of the product of runNo. 4 gave the results set forth in Table III.

In still another illustration, an oxidized hydrocarbon mixture as usedin Table I was mixed with Table III Distillate yields Total yieldsFraction up to 170 C. at Fraction from -170" Fraction from 220 0.1 mm.pressure- C. at 0.2 mm. pres- C. at 0.6-2.0 mm. pres- Acid Value=9.0;Sap. sure-Acid Value= sure-Acid Value= Value=4l4 12.5; Sap. Value=40646.6; Sap. Value=400 Bottoms (Per Cent by Run Per Cent 01' SaponifiablePer Cent of Per Cent of Per Cent of i e based on Per Cent by Saonifiable Saponifiable Saponifiable g Height of lents m B uiva- V Euiva- E uiva- Charge Re- Distillates Per Cent by lent? (based Per Centby g (based Per Cent by (based covered as plus Bot- Weight of onsaponifi Weight of on saponui Weight of on $3 onifi Distillates toms(based Charge able Eqmw Charge able E Charge able uh B 33 gg g g figg:alents in alent s in a1ent s in a1 in Charge) Charge) Charge) Charge) 394. 5 91. 2 62.8 61.4 -1 20. 5 20. 1 11.2 (at 300 C. and 4 m n.pressure) contaming 9.7% of Saponifieble Equivalents of Charge.

Fraction up to 150 C. at Fraction from 170230 In Distil- 0.2 mm.pressure- 0. at 0.6-2.0 mm. preslates only Acid Value= 15.1; Sap.sure-Acid Value= Value=426. 65.4; Sap. Value=408.

4 92. 7 87.0 61. 5 62. 8 l 2 12.0 12. 0 12.2 7.0 (at 340 C. and 2 mm.

pressure).

As another illustration, an oxidized hydrocarbon mixture, as used inTable I, was mixed with an amount of butanol double the theoreticalequivalent based on the saponification value of 75 of alcohol hadoccurred to the extent C. with continuous withdrawal of water formedduring the reaction. Analysis of the reaction product (run No. 6) showedthat combination of 126.0%

based on the theoretical equivalent of the acid value of the oxidizedhydrocarbon. The reacbon mixture. Distillation of the reaction product(run No. 7) gave the results set forth in Table VI:

Table VI Distillate yields Total yields Fraction up to 120 C.Frectionfrorn 120170C. Fraction from 170240 C.

at 1.5-0.1 mm. presat 0.2 mm. pressureat 0.2-4.0 mm. pressureAcidValue=5.8; Acid Volue=6.2; Sap. sure-Acid Value=9.0; Sap. Value=36lValue=4l8 Sap. Value=404 Run Bottoms (Per Cent No. iggf Per Cent of PerCent of Per Cent of by gg? balsed Per Cent by i F Saponifi- Saponifi-Saponifiarge Weight of able Equivable Equivable Equiv- Chorge Re-Distillates Per Cent by alents (oas- Per Cent by alents (bos- Per Centby alcnts (hascovered as (bas'ed 6 Weight of ed on 821- Weight of ed on821- Weight of ed on Sa- Distillates qa Onifi Charge ponifieble Chargeponifiable Charge ponifiable and Botfi uiw Equiva- Equiva- Equivatoms219mg in lents in lents in lents in Charge) Charge) Charge) Charge) 789.7 79.0 28.8 27.9 30.0 33.6 20.6 17. 10.3 (at 320 C. and 4 mm.pressure).

An oxidized hydrocarbon mixture as used in Table I was mixed with anamount of butanol tion product, upon being subjected to distillation,gave the following results (Table V) Table V Distillate yields 'Iotalyields Fraction up to 150 0. at Fraction from 150-170 0. Fraction from170-230 C. at 0.1 mm. pressureat 0.1 mm. pressure at 0.84.5 mm. pres-Acid Value=0.3; Sap. Acid Value=0.3; Sap. sure-Acid Value= Veluc=296Value=274 11.2; Sap. Value=252 Run Bottoms (Per Cent by No. g g ig fWeight based on Charge) Percent by Equivalents Per Cent 01' Per Cent ofPer Cent 01 Weight of innisfinates Saponfiable Saponfiablc SaponilableCharge Re- Per Cent by Equivalents Per Cent by Equivalents Per Cent byEquivalents covered as g (based Weight of (based on Weight of (based onWeight of (based on Distillates on Charge Saponfiable Charge SaponfiableCharge Saponfiable and able uivm Equivalents Equivalents EquivalentsBottoms lentgin in Charge) in Charge) in Charge) Charge) 6 96.3 89.911.2 11.3 43.2 41.5 29.8 25. 7 12.1 (326 C. at 1.5 mm. containing 10.4Per Cent of Saponfieble Equivalents in Charge).

An oxidized hydrocarbon mixture, as used in Table I, was mixed with 10%by weight of Zeo- Karb H and an amount of butanol double the theoreticalequivalent based on the saponification value of the oxidizedhydrocarbon, Zeo- Karb H being an ion-exchange catalyst known to the artand understood to comprise carbon treated with sulfuric acid. Theresulting mixture was heated for 12 hours at 140 to 150 C. withcontinuous Withdrawal of Water formed during the reaction. Analysis ofthe reaction product showed that alcohol combination had been effectedto the extent of 128.5% of the equivalent double the theoreticalequivalent based on the saponification value of the oxidized hydrocarbonmixture and 10% by weight of concentrated sulfuric acid. The resultingmixture was heated for 5 hours at to C. with continuous withdrawal ofwater formed during the reaction. Upon analysis, the reaction product(run N0. 8) showed that alcohol combination had been efiected to theextent of based on the theoretical equivalent of the acid value of theoxidized hydrocarbon mixture. Distillation of the reaction product gavethe results set forth in based on the acid value of the oxidizedhydrocar- Table V11.

Table VII Distillate yields Totalyiclds Fraction up to C. Fraction from150- Fraetion from at 0.2 mm. prcssure 170 C. at 0.2 mm. 234 C. at0.2-5.0 rum. Acid Value= 5.0; Sap. pressureAcid Value= pressurwAcidvalue: Valuo=452 1.6; Sap. Valuo=424 33.6; Sap. Valuc=389 Bottoms (percent by s}? Per cent of Weight based 1 Percent by Per cent of Per centof Per cent of on Charge) W eight of Saponifiablo SaponifiableSaponifieblc Charge B Per cent Equivalents Per cent Equivalents Per CentEquivalents Recovered g (bqywd by Weight (based on by Weight (based onby Weight (based on Distil- 2 g1 of Charge Saponifiahle of ChargeSaponifiablc of Charge Saponifiable letes and h Equivalents EquivalentsEquivalents Bottoms Equivalents in Charge) in Charge) in Charge) inCharge) 8 86. 3 89. 4 40. 3 52. 8 12. 9 13. 4 l6. 5 15.7 7.6 (at 332 C.ands mm.

pressure; containing 7.5 per cent of saponifiable equivalents based onsaponifiable equivalents in Charge).

'11 Anoxidized hydrocarbon mixture as used in Table I was mixed with'2-ethylhexanol in an amount double the theoretical equivalent based 1L2the utilization of such oxidized hydrocarbon mixtures for recovery ofsaponifiable constituents thereof.

- Percent of saponig g'g g g fl fiable Equivalents alent based on Acidin DiSunau-A's based Run No. Charge to Distillation Catalyst onSaponrfiable Value of Oxidized E uivalents m Hydrocarbon g (BottomsMlxture) excluded) 7 l Oxidized hydrocarbon mixtures per se 68. 5 2Butanol treated oxidized hydrocarbon mixture" 83. 5 3... Butanol treatedoxidized mixture 4. 5. do 83.7 6..- Z-ethylheximol treated oxidizedhydrocarbon H1804 79. 5

mixture. 7 Butauol treated oxidized hydrocarbon mixture" ZeoKarb H" 79.08 do H2 04 81. 9

on the saponification value of the oxidized hydrocarbon and heated at154 to 211 C. for 18 hours with continuous withdrawal of water formed.The reacted mixture was then mixed with 0.5% by weight (based on theoxidized hydrocarbon) of zinc chloride and heated for 7 hours at 208 to212 C. with periodic withdrawal of Water formed. Analysis of the thustreated product showed that alcohol combination had been effected to theextent of 118.5% of the theoretical equivalent based on the acid valueof the oxidized hydrocarbon mixture. In still another example, anoxidized hydrocarbon mixture, prepared by oxidizing scale wax (105 to108 F. melting point) in the manner set forth in copending applicationSerial No. 625,961 (now U. S. Patent No. 2,486,454) and having an acidvalue of 369.6 and saponification value of 588.0 was mixed with anamount of 'z-ethylhexanol double the theoretical equivalent based on thesaponification value and with 0.5% (by weight of the oxidizedhydrocarbon) of toluene sulfonic acid. The resulting mixture was heatedfor 4 hours at 145 to 200 C. with continuous withdrawal of water formed.Analysis of the reaction product showed that alcohol combination waseffected to the extent of 123.0% of the theoretical equivalent based onthe acid value of the oxidized hydrocarbon mixture. Similarly to theresults set forth with respect to the examples set forth in theforegoing tables, theaforesaid reaction products prepared with use ofzinc chloride or toluene sulfonic acid, respectively, as catalystsprovided alcohol reacted products which, upon distillation, gaveimproved yields ofsaponifiable equivalents in the form of distillates ascompared to the distillates recoverable by c distillation of theoxidized hydrocarbon mix tures per se without use of an alcoholtreatment run Nos. 2 to 8, inclusive, that practice of the presentinvention'improves the susceptibility of the oxidized hydrocarbonmixtures to distillation with markedly improved yields of saponifiableequivalents in highly desirable distillate form thereby representing amarked improvement in As is apparent from the foregoing illustrations,the markedly improved results embodied by practice of this invention areobtainable by use of a variety of catalytic materials includinginorganic and organic acids, such as sulfuric acid, hydrochloric acid,and toluene sulfonic acid, ion exchange catalysts, e. g., ZeoKarb H, andother catalytic substances such as boron trifluoride etherate, and zincchloride. Although such catalysts have been set forth as specificillustrations in describing the invention, other substances includingmetal oxides such as alumina, silica, mixtures thereof, etc. may beemployed during the treatment of the oxidized hydrocarbon asaforedefined. Hence, in broad aspect the present invention embodies theuse of a catalyst that performs satisfactorily to enhance combination ofthe hydroxyl-bearing compound with an amount of saponifiable groups inthe oxidized hydrocarbon mixture in excess of the theoretical equivalentbased on the acid value. Since substances included in the aforesaidillustrations are known catalysts for esterification reactions, andperform satisfactorily in practice of this invention, it is apparentthat the present invention also contemi plates use of esterificationcatalysts capable of tion of the oxidized hydrocarbons may be morereadily effected to the extent of combining with an amount of thehydroxyl-bearing compound in excess of the theoretical equivalent basedon the acid value whereby saponifiable groups that are not readilycombinable are combined with the hydroxyl-bearing compound to providereaction products that contain saponifiable groups combined with thehydroxyl-bearing compound, in

admixture with saponifiable groups that are not so combined, the amountof saponifiable groups thus combined being in excess of the saponifiablegroups accounting for the acid value of the oxidized hydrocarbon mixturesubjected to the treatment of this invention. That such case ofcombination may be effected is clearly an unexpected result,particularly when it is considered that same is effected without need ofpretreating the oxidized hydrocarbon mixture for removal of certainsaponifiable or unsaponifiable constituents prior to reaction with thehydroxyl-bearing compound. This is further surprising inasmuch as, inthe absence of a catalyst, the oxidized hydrocarbon mixtures, asembodied for use herein and which contain saponifiable groups giving anacid value in admixture with saponifiable groups that account for thedifierence between acid and saponifiable value, show a marked resistanceto combining with an amount of the hydroxyl-bearing compound in excessof the theoretical equivalent based on the acid value. Not only does theuse of a catalyst facilitate such extensive combination but,additionally, generally enables the attainment thereof at lowertemperatures and/or shorter reaction periods than treatment of theoxidized hydrocarbon in the absence of a catalyst and although, even byuse of higher temperature and longer reaction periods in the absence ofthe catalyst, combination is not generally, if at all, effected past theacid value of the oxidized hydrocarbon.

As is apparent from the foregoing, and as compared to the oxidizedhydrocarbon mixtures per se, treatment of such mixtures in accordancewith this invention not only improves the sus-- ceptibility of suchmixtures for treatment by distillation with improved recovery ofsaponifiable equivalents in desirable distillate form, but, ofconsiderable importance, use of a catalyst in some manner facilitatescombination of a suitable hydroxyl-bearing compound with saponifiablegroups in an amount substantially in excess of the theoreticalequivalent based on the acid value. Thus, by practice of this invention,combination is readily effected with free acid groups as well as with asubstantial portion of saponifiable groups that are not in free acidform, the latter groups accounting for the difference between the acidand saponification value of the oxidized hydrocarbon mixture. Asaforesaid, attainment of combination to such an extent is clearlunexpected andis especially so when it is considered that by practice ofthis invention such combination occurs even though the crude oxidizedhydrocarbon mixtures subjected to treatment contain saponifiable groups(accounting for the difference between acid and saponification value)that offer a marked resistance to combining with a hydroxyl-bcaringcompound containing a hydroxyl group possessing alcoholiccharacteristics. Thus, the results obtained by practice of thisinvention, and using oxidized hydrocarbon mixtures as aforedefined, areclearly unexpected and are not predictable from prior art knowledge ofwhich we are aware relating to reactions (e. g., 5,

such as esterification) of alcoholic substances with acids, includingacids separated out of oxidized hydrocarbon mixtures, and which aredevoid of or do not contain substantial amounts of intermediatelyoxidized compounds that account for a diiference between an acid andsaponification value and which oiier a marked resistance to combiningwith alcoholic substances. However, by use of a catalyst in thetreatment disclosed herein, an unexpected function is provided in thatduring the reaction certain constituents of the oxidized hydrocarbonmixture are in some manner altered whereby certain of the saponifiablecompounds that offer a marked resistance to combining with an alcoholiccompound are converted to a combinable form resulting. in increasedyields of desired reaction products.

The reaction products obtained by treatment of oxidized hydrocarbonmixtures in accordance with this invention are, as far as we are aware,

novel compositionshaving utility for many purposes- In particlular, thereaction products, and distillates obtainable therefrom, such as thereaction products and distillates disclosed. hereinbefore, are highlyuseful as organic solvents, as intermediates for preparation of chemicalderivatives of the constituents of the reaction products and distillatestherefrom, and as addition agents for substances such as syntheticresins for plasticizing and other purposes.

Although the present invention has been described in conjunction withcertain preferred embodiments thereof, those skilled in the art 'willreadily recognize that variations and modifications can be made. Suchvariations and modifications are to be considered to be within thepurview of the specification and the scope of the appended claims.

We claim:

1. An improved method for treatment of an oxidized hydrocarbon mixture,as defined hereinaiter, to promote combination between a substantialportion of the saponifiable groups accounting for the difference betweenthe acid and saponification value with an organic compound containing ahydrcxyl group possessing alcoholic characteristics, said oxidizedhydrocarbon mixture being characterized by having a saponification valueof over 400, a substantial difference between acid and saponificationvalue, and prepared by liquid phase oxidation of hydrocarbons withoxygen of a free oxygen containing gas, which comprises reacting anoxidized hydrocarbon mixture of the aforesaid characteristics with anorganic compound containing a hydroxyl group possessing alcoholiccharacteristics for a period of time sufficient to combine with saponifiable groups of said mixture an amount of said alcoholic compound inexcess of the theoretical equivalent based on the acid value of said mixture, said reaction being carried out in the presence of anesterification catalyst capable of causing said reaction to continuebeyond the extent of combining said alcoholic compound in an amounttheoretically equivalent to the acid value of said mixture whereby asubstantial portion of the saponifiable groups accounting for thedifference between the acid and saponification values of said mixtureare combined with said alcoholic compound.

2. A method, as defined in claim 1., wherein the catalyst is an acidiccatalyst.

3. A method, as defined in claim 1, wherein the hydroxyl-containingcompound is an alcohol.

4. A method, as defined in claim 1., wherein the hydroxyl-containingcompound is an aliphatic monohydric alcohol.

5. An improved method for treatment of an oxidized hydrocarbon mixture,as defined hereinafter, to'promote combination between a substantialportion of the saponifiable groups accounting for the difierence betweenthe acid and saponification values of said mixture with a monohydricaliphatic alcohol, said oxidized hydrocarbon mixture being characterizedby having a saponification value of over 400, a substantial diiie'rencebetween acid and saponification value, and prepared by liquid phaseoxidation of hydrocarbons with oxygen of afree oxygen containing gas,which comprises preparing a reaction mixture comprising an oxidizedhydrocarbon mixture of the aforesaid characteristics and an amount of amonohydric alcohol substantially in excess of the theoretical equivalentbased on the acid value of the oxidized hydrocarbon mixture, and heatingsaid reaction'mixture in the presence of an acidic catalyst whilewithdrawing water formed during reaction of the oxidized hydrocarbonwith the alcohol to promote combination of said oxidized hydrocarbonwith an amount of said alcohol in excess of the theoretical equivalentbased on the acid value of the oxidized hydrocarbon mixture.

6. As a new composition, a reaction product formed by reaction of anorganic compound containing a hydroxyl group possessing alcoholiccharacteristics with an oxidized hydrocarbon mixture having asaponification value of over 400, a substantial diiference between theacid and saponification value, and prepared by liquid phase oxidation ofhydrocarbons with oxygen of a free oxygen containing gas, said reactionproduct being characterized by containing saponifiable groups incombination with said hydroxylbearing compound and saponifiable groupsthat are not combined with said hydroxyl-bearing compound, said reactionproduct being further characterized in that the amount of saponifiablegroups thereof combined with said hydroxylbearing compound is in excessof the theoretical equivalent based on theacid value of said oxidizedhydrocarbon mixture.

7. An improved method for treatment of an oxidized hydrocarbon mixtureas defined hereinafter to promote combination between a substantialportion of saponifiable groups accounting for the difierence between theacid and saponification values of said oxidized hydrocarbon mixture withan organic compound containing a hydroxyl group possessing alcoholiccharacteristics, said oxidized hydrocarbon mixture being characterizedby having a substantial difference between its acid and saponificationvalue and prepared by contacting hydrocarbons in liquid phase at anoxidizing temperature-with a gas containing free oxygen to combineoxygen with the hydrocarbons at an average rate related to the oxidizingtemperature as follows: substantially above 1.5 liters of oxygen perhour per kilogram of hydrocarbons at an oxidizing temperature of 120 C.,substantially above 23 liters of oxygen per hour per kilogram ofhydrocarbons at an oxidizing temperatureof 160 0., and substantiallyabove 135 liters of oxygen per hour per kilogram of hydrocarbons at anoxidizing temperature of 180 C., which comprises reacting an oxidizedhydrocarbon mixture of the aforesaid characteristics with anorganic'compound containing a hydroxyl group possessing alcoholiccharacteristics for a period of time sufficient to combine with saidsaponifiable groups of said mixture an amount of said alcoholic.compound in excess of the theoretical equivalent based on the acid valueof said mixture, said reaction being carried out in the pres-.- ence ofan esterification catalyst capable of causing said reaction to continuebeyond the extent of combining said alcoholic compound in an amounttheoretically equivalent to the acid value of said mixture whereby asubstantial portion of the saponifiable groups accounting for thedifierence between the acid and saponification values of said mixtureare combined with said alcoholic compound.

8. A method, as defined in claim 7, wherein the oxidized hydrocarbonmixture has a saponification value of over 400.

9. A method, as defined in claim 7, wherein the hydroxyl-bearingcompound is an alcohol.

10. A method, as defined in claim 7, wherein the'hydroxyl-bearingcompound is an aliphatic monohydric alcohol. Y

11. A method, as defined in claim '7, wherein the catalyst is an acidiccatalyst.

12. A reaction product, prepared by the metho of claim 7, characterizedby containing saponifiable groups combined with the hydroxyl-bearingcompound and saponifiable groups uncombined with said compound, saidreaction product being further characterized in that the amount ofsaponifiable groups combined with said hydroxyl-bearing compound is inexcess of the saponifiable groups accounting for the acid value of theoxidized hydrocarbon mixture subjected to z the treatment of claim 7.

13. An improved method for treatment of an oxidized hydrocarbon mixtureas defined hereinafter to promote combination between a substantialportion of the saponifiable groups'accounting for the difference betweenthe acid and saponification value of said mixture with a monohydricaliphatic alcohol, said oxidized hydrocarbon mixture being characterizedby having a saponification value of over 400, a substantial diiferencebetween its acid and saponification value, and prepared by contactinghydrocarbons in liquid phase at an oxidizing temperature with a gascontaining free oxygen to combine oxygen with the hydrocarbons at anaverage rate related to the oxidizing temperature as follows:substantially above 1.5 liters of oxygen per hour per kilogram ofhydrocarbons at an oxidizing temperature of C., substantially above 23liters of oxygen per hour per kilogram of hydrocarbons at an oxidizingtemperature of C., and substantially above 135 liters of oxygen per hourper kilogram of hydrocarbons at an oxidizing temperature of C., whichcomprises preparing a reaction mixture comprising said oxidizedhydrocarbons and a monohydric aliphatic alcohol in an amountsubstantially in excess of the theoretical equivalent based on the acidvalue of the oxidizedhydrocarbon, and heating said reaction mixture inthe presence of an acidic catalyst while withdrawing water formed byreaction of the oxidized hydrocarbon with the alcohol to promotereaction between said oxidized hydrocarbon and an amount of alcohol inexcess of the theoretical equivalent based on the acid value of theoxidized hydrocarbon mixture.

14. A method, as defined in claim-13, wherein the reaction product issubjected to fractional distillation.

15. A method for treatment of an oxidized hydrocarbon mixture as definedhereinafter to improve the susceptibility thereof to treatment bydistillation with improved recovery of saponifiable equivalents indistillate form, said oxidized hydrocarbon being characterized by havinga saponification value of over 400, a substantial difference betweenacid and saponification value, and prepared by liquid phase oxidation byhydrocarbons with oxygen of a free oxygen containing gas, whichcomprises preparing a reaction mixture containing an oxidizedhydrocarbon of the aforesaid characteristics and an organiccompoundcontaining a hydroxyl group possessing alcoholic characteristicsand heating said reaction mixture in the presence of an esterificationcatalyst capable of causing said reaction to continue until saponofiablegroups of said mixture have combined with an amount of said alcoholiccompound in excess of the theoretical equivalent based on the acid valueof said mixture.

16. An improved method for treatment of an oxidized hydrocarbon mixtureas defined hereinafter to promote combination between a substantialportion of the saponifiable groups accounting for the difference betweenthe acid and saponification value of said mixture with an organiccompound containing a hydroxyl group possessing alcoholiccharacteristics, said oxidized hydrocarbon mixture being characterizedby having a saponification value of over 400, a substantial difierencebetween acid and saponification value, and prepared by liquid phaseoxidation of hydrocarbon with oxygen of a free oxygen containing gas,which comprises reacting an oxidized hydrocarbon mixture of theaforesaid characteristics with an organic compound containing a hydroxylgroup possessing alcoholic characteristics to combine with said oxidizedhydrocarbon an amount of said hydroxyl-bearing compound theoreticallyequivalent to a substantial portion of the acid value of said oxidizedhydrocarbon mixture and then continuing to react the product of theaforesaid reaction with a hydroxyl-bearlng compound as aforesaid in thepresence of an esterification catalyst capable of causing said reactionto continue beyond the extent of combining the alcoholic compound in anamount theoretically equivalent to the acid value of said mixture andcombine with said alcoholic compound a substantial portion of thesaponifiable groups accounting for the difference between the acid andsaponification values of said mixture to produce an oxidized hydrocarbonmixture having a substantial portion of its saponifiable groupsaccounting for the difference between its acid and saponiflcation valuein combination with said hydroxyl-bearing compound.

17. A method, as defined in claim 1, wherein the oxidized hydrocarbonmixture had been prepared by oxidation of a predominantly parafilnichydrocarbon mixture, the organic compound is 18 a monohydric aliphaticalcohol, and the catalyst is an acidic catalyst.

18. A method, as defined in claim 17, wherein the catalyst is a memberfrom the group consisting of sulfuric acid, hydrochloric acid, toluenesulfonic acid, zinc chloride and boron trifluoride etherate.

19. A method, as defined in claim 7, wherein the catalyst is an acidiccatalyst, the organic compound is a monohydric aliphatic alcohol, andthe oxidized hydrocarbon mixture had been prepared by oxidation of apredominantly paraffinic hydrocarbon mixture.

20. As a new composition, a reaction product formed by reaction of analiphatic monohydric alcohol with an oxidized hydrocarbon mixture havinga saponification value of over 4100, a substantial difference betweenthe acid and sapom'fication value, and prepared by liquid phaseoxidation of a predominantly paraffinic hydrocarbon mixture with oxygenof a free oxygencontaining gas, said reaction product beingcharacterized by containing saponifiable groups in combination with saidalcohol and saponifiable groups that are not combined with said alcohol,said reaction product being further characterized in that the amount ofsaponifiable groups thereof combined with said alcohol is in excess ofthe theoretical equivalent based on the acid value of said oxidizedhydrocarbon mixture.

CARL N. ZELLNER. FRED LISTER.

REFERENCES CITED The following references are of record in the Name DateJahrstorfer et a1. Sept. 22, 1936 Number

1. AN IMPROVED METHOD FOR TREATMENT OF AN OXIDIZED HYDROCARBON MIXTURE,AS DEFINED HEREINAFTER, TO PROMOTE COMBINATION BETWEEN A SUBSTANTIALPORTION OF THE SAPONIFIABLE GROUPS ACCOUNTING FOR THE DIFFERENCE BETWEENTHE ACID AND. SAPONIFICATION VALUE WITH AN ORGANIC COMPOUND CONTAINING AHYDROXYL GROUP POSSESSING ALCOHOLIC CHARACTERISTICS, SAID OXIDIZEDHYDROCARBON MIXTURE BEING CHARACTERIZED BY HAVING A SAPONIFICATION VALUEOF OVER 400, A SUBSTANTIAL DIFFERENCE BETWEEN ACID AND SAPONIFICATIONVALUE, AND PREPARED BY LIQUID PHASE OXIDATION OF HYDROCARBONS WITHOXYGEN OF A FREE OXYGEN CONTAINING GAS, WHICH COMPRISES REACTING ANOXIDIZED HYDROCARBON MIXTURE OF THE AFORESAID CHARACTERISTICS WITH ANORGANIC COMPOUND CONTAINING A HYDROXYL GROUP POSSESSING ALCOHOLCHARACTERISTICS FOR A PERIOD OF TIME SUFFICIENT TO COMBINE WITHSAPONIFIABLE GROUPS OF SAID MIXTURE AN AMOUNT OF SAID ALCOHOLIC COMPOUNDIN EXCESS OF THE THEORETICAL EQUIVALENT BASED ON THE ACID VALUE OF SAIDMIXTURE, SAID REACTION BEING CARRIED OUT IN THE PRESENCE OF ANESTERIFICATION CATALYST CAPABLE OF CAUSING SAID REACTION TO CONTINUEBEYOND THE EXTENT OF COMBING SAID ALCOHOLIC COMPOUND IN AN AMOUNTTHEORETICALLY EQUIVALENT TO THE ACID VALUE OF SAID MIXTURE WHEREBY ASUBSTANTIAL POR TION OF THE SAPONIFIABLE GROUPS ACCOUNTING FOR THEDIFFERENCE BETWEEN THE ACID AND SAPONIFICATION VALUES OF SAID MIXTUREARE COMBINED WITH SAID ALCOHOLIC COMPOUND.